Iridate Li₈IrO₆: An Antiferromagnetic Insulator

A polycrystalline iridate Li₈IrO₆ material was prepared via heating Li₂O and IrO₂ starting materials in a sealed quartz tube at 650 °C for 48 h. The structure was determined from Rietveld refinement of room-temperature powder neutron diffraction data. Li₈IrO₆ adopts the nonpolar space group R3̅ with Li atoms occupying the tetrahedral and octahedral sites, which is supported by the electron diffraction and solid-state ⁷Li NMR. This results in a crystal structure consisting of LiO₄ tetrahedral layers alternating with mixed IrO₆ and LiO₆ octahedral layers along the crystallographic c-axis. The +4 oxidation state of Ir⁴⁺ was confirmed by near-edge X-ray absorption spectroscopy. An in situ synchrotron X-ray diffraction study of Li₈IrO₆ indicates that the sample is stable up to 1000 °C and exhibits no structural transitions. Magnetic measurements suggest long-range antiferromagnetic ordering with a Néel temperature (T_N) of 4 K, which is corroborated by heat capacity measurements. The localized effective moment μ_eff (Ir) = 1.73 μ_B and insulating character indicate that Li₈IrO₆ is a correlated insulator. First-principles calculations support the nonpolar crystal structure and reveal the insulating behavior both in paramagnetic and antiferromagnetic states.